Substituted 1,3,5-triazinyl-(6)-aminophenyl-arsenic compounds



Patented Dec. 4, 1945 UNITED STATES PATENT OFFICE SUBSTITUTED 1,3,5-TRIAZINYL- (6) -AMINO- PHENYL-ARSENIC COMPOUNDS Ernst A. H. Friedheim, New York, N. Y.

No Drawing. Application June 3, 1944, Serial No. 538,697

'7 Claims.

with an aromatic organic compound containing trivalent arsenic and corresponding to the formula WC6H2 (A B)-AS=X In these formulas, W is an amino-group or halogen. If W is an amino-group, at least one of the groups D. E, F, is a halogen-group. If W is a halogen, at least one of the groups D, E, F is an amino-group. In both cases the other groups are selected from the group consisting of halogen, NHz, NH. Alk.. N Alk.2, hydroxy-alkyl-amino, N'HCHzCHOHCHzOI-I, dialkyl-amino-alkyl-amino. and aminoacyl radicals, such as NHCOCHa and NHCOCeH; the radicals A and B are selected from the group consisting of hydro en,

halo en, OH, O Alk., O acyl. N02, NI-Iz. NH Alk., N A1k.2, aminoacyl, and alkyl radicals, X is a divalent group selected from the group consisting of O, S, dihalides, such as C12, I2 or Bra, and.-

sulfur-containing radicals of the type =(SR)s wherein R is an organic radical which is capable of carrying a SH-radical. Such sulfur-containing reactants are, for example, thioglycolic acid, cysteine. or lutathione. thiophenol. As examples of the trivalent arsenic compounds to be used according to my invention. the following may be mentioned: l-amino-phenylarsinoxide, 4-chlorphenyl-arsinoxide, i-amino-phenyl-arsindichloride, 4-amino-phenyl-arsinsulfide, 3-amino-4- oxy-phenylarsinoxide.

The condensation products thus formed have the formula CNHC;H(A,B)AS=X wherein Y and Y are each a radical selected from the group consisting of halogen, NI-I2. NH Alk., N Alk.2, hydroxy-alkyleamino,

NHCHzCHOHCHzOH dialkyl-amino-alkyl-amino, and aminoacyl radicals; A and B are selected from the group consisting of hydrogen, halogen, OH, 0 A1k., O acyl, N02, NI-I2, NH Alk., N Alk.z, amino-acyl, and alkyl radicals, and X is a divalent radical selected from the group consisting of O, S, dihalides. sulfur-containing groups of the type (S-R) 2, wherein R is an organic radical which is capable of carrying a SH-radical, and groups having the formula In carrying out the present invention, for example an aqueous solution containing one mol of 4-oxy-3-aminoephenyl-arsinoxide may be caused to react with a fine suspension of 1 mol of 2,4,6- trichloro-1,3,5-triazine in water at a temperature of 0 C. with the exclusion of oxygen. The resulting condensation product has the formula AFO Subsequently, this reaction product may be treated with a base selected from the group consisting of ammonia, alkyl amines, hydroxy-alkyl amines and dialkyl-amino-alkyl amines. Similar reactions may be obtained by using a dihalide such as 4amino-phenylarsindichloride instead of 4-oxy-3-amino-phenylarsinoxide. Instead of the latter, its derivatives or isomers, such as, for

instance, 2-oxy-4-amino-pheny1 arsinoxide, 01 4- amino-3-oxy-pheny1arsinoxide may also be used. In carrying out these reactions, instead of the trichloro-triazine other derivatives of 1,3,5-triazine corresponding to the formula referred to above may also be used.

I have further found that the condensation products according to this invention may also be obtained by first forming a condensation product of the type disclosed in my above mentioned U. S. Patent No. 2,295,574 from a derivative of 1,3,5- triazine and a substituted phenyl-arsonic acid,

and converting the condensation product thus obtained, into a compound containing trivalent arsenic. I have found that such conversion can be performed without the disintegrationof the basic triazinyl-aminobenzene structure by treating the triazinyl-aminobenzene-arsonic acid condensation product in hydrochloric acid solution, in the presence of hydriodic acid, with $02, hypophosphorous acid (H2PO3), orstannous chloride, or in neutral or alkaline solution with phenylhydrazine or sodium hydrosulfite (Na-25204). The reduction with $02 or phenylhydrazine leads to the arsinoxides, or dihalogenarsines, whilethe treatment with stannous chloride,'hypophosphorous acid, and sodium hydrosulfite leads tothe corresponding arseno-compounds.

For example, one part by weight of 2-,4-diamino- 1,3,5 triazinyl (6) [amino 3 oxy -A- phenylarsonic acid I] is dissolved at about.-80 C. in 100 parts of hydrochloric acid of sp. gr. 1.19. To the -clear,-warm solution V part .of: sodium iodide is -added,:and a-stream of '80: gas .is allowed to pass through the solution. After a few minutes the solution becomes cloudy, and the hydrochloride of ZA-dia-mino-1',3,5 triazinyl- (6)- oxyaminophenylarsindichloride separates out in crystalline -form. It is soluble in ethyl alcohol -irom which it may be'recrystallized. It is slightly solublejn acetone, and insoluble in chloroform,

CClr-and benzene. The corresponding arsinoxide is-formed by the action-of alkali, such as dilute ammonia or sodiumbicarbonate on the arsindichloride.

An arseno-compound can' be obtained-by'the action of stannous chloride on 2,4-diamino-triazinyl- (6) -[4-oxy-3-aminophenylarsonic acid I]. One part of the latter is suspended in 50 parts of aqueous hydrochloric acid of 1.19 density containing about-50% stannous chloride,-and 1% of hydriodic :acid. On gentle warming the subtance goes. slowly into solution, the reaction mixture -taking ,a .yellow color. It becomes cloudy, and .onstanding a yellow precipitate separates, which represents 3 the hydrochloride of the bis[2;2' 4 4' -t, vtraamino triazinyl -(6 -"6')']- BPS'QdiaminQ-AA' dioyarseno1benzene of the formula ering ,said .diCl'IlQIDtCOIHPQQQ-F with 1 2 325 591 quantity of 10% aqueous ammonia, and shaking at 45 C. for 1 hour, whereby the product goes .into completesolution. By heating the [Z-chlor0 --4 amino 1,3,5 triazinyl (6)] aminophenyl-arsonic compound in hydrochloric acid .solution with S02, a compound of the formula ism-H01 2C 10 Cl( 3 g-NHOAFO s may be obtained.

By'reacting an aqueous alkaline solution con- ..taining one mol of -3,5-dinitro-4-amino-phenyl- ,arsonicacid of the formula JIITH:

: VO:N NO:

with a fine suspension of 1 mol of 2,4,6-trichloro- 1,3,5-triazine in water at a temperature of 0 C., a condensation product corresponding to the formula is obtained. This compound may be converted by reduction with stannous chloride in aqueous hydrochloric acid solution into a compound corresponding ,to the formula fiimilar compounds-may be obtained by reacting other aminophenyl arsonic acids further sub- .-stitutedin'thebenzene ring by two aminogroups pr two nitro groups or-by one amino and one nitrogroup,-with cyanuric chloride in the above described manner-and subjecting the resulting .triazine derivative to reduction in hydrochloric :acid solution by means of stannous chloride-or-by theaction'of-sOzlgas in-the presence of hydriodic v aci Reference is made to my co-pending application Ser. 'No. 422,234 filed on December 9, 1941, of which thisisa continuation-impart.

It is to be understoodthat in the above'specification and the appended claims the term amino radical or amino radicals is used to :include -NH2 radicals as well as-the above disclosed substituted amino radicals.

claim: 1. A 1,3,5-triazine derivative of the-formula 7 5 c herein and Y: eachrepresent al-halogenica is a benzene ring, A and B are amino radicals, and

X is a divalent radical selected from the group wherein C6 is a benzene ring, A and B are amino radicals, and X is a divalent radical selected from the group consisting of O, S, and dihalides. 3. A 1,3,5-triazine derivative of the formula wherein C6 is a. benzene ring, and X is a divalent radical selected from the group consisting of O, S and dihalides.

4. A 1,3,5-triazine derivative of the formula f NH:

i 01-0 c-NH AsOln 5. A process for preparing a 1,3,5-triazine derivative as claimed in claim 1, said process comprising reacting a compound of the formula H2NCeH2(A,B')-ASO3H2, wherein A and B are selected from the group consisting of nitro, and amino groups, with cyanuric chloride and subjecting the resulting condensation product to the action of a reducing agent.

' 6. A process for preparing a 1,3,5-triazine derivative as claimed in claim 1, said process comprising reacting a compound of the formula HzNCsHz(A,B')-AsO3H2, wherein A and B are selected from the group consisting of nitro, and amino groups, with cyanuric chloride and subjecting the resulting condensation product to reduction with stannous chloride in hydrochloricacid solution.

7. A process for preparing a 1,3,5-triazine derivative as claimed in claim 1, said process comprising reacting a compound of the formula H2NC6H2(A',B')ASO3H2, wherein A and B are selected from the group consisting of nitro, and amino groups, with cyanuric chloride and subjecting the resulting condensation product to 5 reduction by means of S02 gas in the presence of hydroiodic acid in hydrochloric acid solution.

ERNST A. H. FRIEDHEIM. 

